GB2086597A

GB2086597A - Colour photographic light-sensitive material

Info

Publication number: GB2086597A
Application number: GB8124529A
Authority: GB
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1980-08-12
Filing date: 1981-08-11
Publication date: 1982-05-12
Also published as: DE3131926A1; JPS6116063B2; JPS5735858A; US4351897A; US4351897B1; DE3131926C2; GB2086597B

Description

1

SPECIFICATION

Color photographic light-sensitive material GB 2 086 597 A 1 The present invention relates to a color photographic light-sensitive material, and more particularly to a 5 silver halide color photographic light-sensitive material wherein the magenta dye formation efficiency in the color development step is high, photographic properties are not influenced by variations in the pH of the color development bath, and the color images are fast to heat or light.

Various pyrazolone derivatives have been known as magenta color imageforming couplers (referred to hereinafter simply as "magenta couplers"). However, these pyrazolone derivatives generally have low color 10 formation efficiency (ratio of conversion of the coupler into a dye) when contained in photographic light-sensitive materials, and so-called 4-equivalent couplers, in which the coupling position is not substituted, usually have from only about 1/2 mol of dye per mol of the coupler.

To improve color formation efficiency, so-called 2-equivalent magenta couplers have been used, in which a substituent is introduced into the coupling position of a pyrazolone type magenta coupler, and the 15 substituent splits off in the color development step. Exampls of such couplers are disclosed, for example, in U.S. Patents 3,311,476,3,419,391, 3,617,291, and 3,926,631. Further, magenta couplers in which a substituent is linked to the coupling position through sulphur ion are described in U.S. Patent 3,214,437 (a thiocyano group), U.S. Patent 4,032, 346 (an acylthio group or a thioacylthio group), U.S. Patents 3,227,554 and 3,701,783 and Japanese Patent Publication No. 34044/78 (an arylthio group or a heterocyclic thio group), 20 and West German Patent Application (OLS) No. 2,944,601 (and alkylthio group).

It has been found as the result of our investigations that when couplers having an arylthio group at the coupling active position among the magenta couplers described in U.S. Patents 3,227,554 and 3,701,783 are used in a color photographic light-sensitive material and color images are formed, the light fastness of the color images does not completely satisfy the desired improvement in the properties of the color photographic light-sensitive materials. Also, it has been found that when the magenta couplers which release an arylthio group as described in Japanese Patent Publication No. 34044/78 are used in a color photographic light-sensitive material and color images are formed, the light fastness of the color images is insufficient. 30 Therefore, a first object of this invention is to provide a color photographic light-sensitive material which 30 forms color images which are fast to light. A second object of this invention is to provide a color photographic light-sensitive material in which photographic properties are less influenced by variations in the pH of the color development bath. A third object of this invention is to provide a color photographic light-sensitive material containing a low cost 2-equivalent magenta coupler by a simple production process.

Afourth object of this invention is to provide a color photographic lightsensitve material having improved color formation efficiency, reduced coupler content, and reduced silver halide content.

The above-described objects of this invention can be effectively attained by incorporating a magenta coupler in which one hydrogen atom on the coupling position of the pyrazolone is substituted by an arylthio group in which at least one of the ortho positions is substituted or a naphthylthio group into a light-sensitive 40 silver halide emulsion layer of a silver halide color photographic light- sensitive material.

More particularly, by using such a magenta coupler, which releases an ortho-substituted arylthio or a naphthylthio group, in a silver halide color photographic light-sensitive material, the following effects can be obtained.

(1) Color images obtained by coupling with an oxidation product of a color developing agent (for 45 example, a p-phenylenediamine type developing agent) are remarkably fast to light or heat.

(2) Color formation efficiency of the magenta coupler is remarkably improved. Accordingly, the amount of magenta coupler used can be reduced as compared with prior art couplers and the amount of silver halide can also be significantly reduced. Consequently, it is possible to reduce the thickness of the magenta color image providing emulsion layer. As a result, the sharpness of images can be significantly improved.

(3) Color photographic light-sensitive materials can be produced at a moderae price with reductions in the amount of coupler and the amount of silver halide used.

(4) The process of color development is stabilized (i.e., light-sensitive materials which are hardly influenced by variation of pH of photographic processing solutions can be obtained).

(5) A color photographic light-sensitive material having stabilized quality can be obtained, in which 55 abnormal coloring during development does not occur when the material is allowed to stand in the presence of formaldehyde before development.

(6) Color photographic light-sensitve materials in which the granularity of color images after development is excellent can be obtained.

The magenta coupler which releases the arylthio group used in the present invention is represented by the 60 following formula (1) or (11):

2 GB 2 086 597 A 2 X R2 H CNH-- (R,) N (R3) M1 J"'N 0 M2 5 1 Ar 1 OR4 10 H NH -1-S (H) 11 1. t,- (R (R1)mI N 0 -15 Ar wherein Ar represents a phenyl group substituted with at least one substituent selected from a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group and a cyano group; X represents a halogen 20 atom or an alkoxy group; R, represents a hydrogen atom, a halogen atom, an alkyl group,-an alkoxy group, an acylarnino-group, a sulfonamido group, a sulfamoyl group, a carbamoyl group, a diacylamino group, an alkoxycarbonyl group, an alkoxysulfonly group, an aryloxysulfonyl group, an alkanesulfonyl group, an aryisuifonlyl group, an alkylthio group, an arylthio group, and alkyloxycarbonylamino group, an alkylureido group, an acyl group, a nitro group, a carboxy group or a trifluoromethyl group; R2 represents a halogen 25 atom, a hydroxy group, an alkyl group, an alkoxy group or an aryl group; R3 represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group or an aryl group; at least one of R2 and R3 represents an alkoxy group; m, and M2 each represents an integer from 1 to 4; R4 represents an alkyl group - or an aryl group; R5 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an aryl group; n represents an integerfrom 1 to 6; and when M1,M2and n each is 2 or more, each R,, R3 and R5 may 30 be the same or different.

The magenta couplers which can be used in the color photographic lightsensitive material of the present invention are capable of drastically improving the lightfastness of the color images. This factcannot be expected from the conventionally known couplers releasing an arylthio group, and is very surprising, as will be apparent from the detailed description hereinafter.

The following description includes the preferred substituents of the couplers.

In formulae (1) and (11), Ar is a substituted phenyl group. The substituent for the phenyl group includes a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom), an alkyl group having from 1 to 22 carbon atoms (for example, a methyl group, an ethyl group, a tetradecyl group, a tert-butyl group), an alkoxy group having from 1 to 22 carbon atoms (for example, a methoxy group, an ethoxy group, an octyloxy group, a dodecyloxy group), an alkoxycarbonyl group having from 2 to 23 carbons atoms (for example, a methoxycarbonyl group, an ethoxycarbonyl group, a tetradecyloxycarbonyl group) or a cyano group.

X in formulae (1) and (11) represents a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom or an aikoxy group having from 1 to 22 carbon atoms (for example, a methoxy group, an 45 octyloxy group, a dodecyloxy group).

R, in formulae (1) and (11) represents a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom), straight chain or branched chain alkyl group (for example, a methyl group, a tert-butyl group, a tetradecyl group), an alkoxy group (for example, a methoxy group, an ethoxy group, a 2-ethylhexyloxy group, a tetradecyloxy group), an acylamino group (for example, an acetamido group, a 50 benzamido group, a butanamido group, a tetradecanamido group, an ct-(2,4di-tert-amy[phenoxy) acetamido group, an a-(2,4-di-tert-amylphenoxy)butyramido group, an a-(3 pentadecylphenoxy)hexanamido group, an ct-(4-hydroxy-3-tertbutylphenoxy)tetradecanamido group, a 2-oxopyrrolidin-l-yi group, a 2oxo-5-tetradecylpyrrolidin-l-yI group, an Wmethyltetradecanamido group), a sulfonamido group (for example, a methanesulfonamido group, a benzenesulfonamido group, a p- -55 toluenesulfonamido group, an octanesulfonamido group, a p- dodecylbenzenesuifonamido group, an N-methy[tetradecanesuifonamido group), a sulamoyl group (for example, an N-methyisulfamoyl group, an N-hexadecyisulfamoyl group, an N-[3-(dodecyloxy)propy[IsulfamoyI group, an W[4-(2,4-di-tert amyiphenoxyi)butyilsulfamoyl group, an N-methyi-N-tetradecyisulfamoyl group), a carbamoyl group (for example, an Wmethylcarbamoyl group, an N-octadecylcarbarnoyl group, an W[4-(2,4-di-tert amyiphenoxy)butyllcarbamoyl group, an N-methyi-N-tetradecylcarbamoyl group), a diacylamino group (for example, an N-succinimido group, an N-phthalimido group, a 2,5-dioxo-1 - oxazolidinyl group, a 3-dodecyl 2,5-dioxo-1 -hydantoinyl group, a 3-(N-acetyi-N-dodecylamino)succinimido group), an alkoxycarbonyl group (for example, a methoxycarbonyl group, a tetradecyloxycarbonyl group, a benzy[oxycarbonyl group), an alkoxysulfonyl group (for example, a methoxysulfonyi group, an octyloxysulfonyl group, atetradecyloxysul- 65 -35 g 3 -5 GB 2 086 597 A 3 fonyl group), an aryloxy sulfonyl group (for example, a phenoxysulfonyl group, a 2,4-di-tertamyiphenoxysuifonyl group), an alkanesulfonyl group (for example, a methanesulfonyl group, an octanesulfonyl group, a 2ethyihexanesuifonyl group, a hexadecanesulfonyl group), an aryisuifonyl group (for example, a benzenesulfonyl group, a 4-nonyibenzenesuifonyl group), an alkylthio group (for example, 5 and ethylthio group, a hexyithio group, a benzyithio group, a tetradecylthio group, a 2-(2,4-ditertamyiphenoxy)-ethyithio group), an arylthio group (for example, a phenylthio group, a p-toiylthio group), an alkyloxycarbonylamino group (for example, an ethyl oxycarbonyla m in o group, a benzyioxycarbonylamino group, a hexadecyloxycarbonylamino group), an alkylureido group (for example, an Wmethylureido group, an N,N-di methyl u reido group, and N-methyl-N-dodecylureido group, an Whexadecylureido group, an -10 N,N-dioctadecylureido group), and acyl group (for example, an acetyl group, a benzoyl group, an octadecanoyl group, a p- dodecanamidobenzoyl group), a nitro group, a carboxy group or a trifluoromethyl group. In the above-described substituents, the alkyl moieties thereof preferably have from 1 to 36 carbon atoms, and the aryl moieties thereof preferably have from 6 to 38 carbon atoms.

R2 in formula (1) represents a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom), a hydroxy group, an alkyl group having from 1 to 22 carbon atoms (for example, a methyl group, an 15 ethyl group, a tert-butyl group, a 1,1,3,3-tetramethyibutyl group, a 2-(2, 4-di-tert-amyiphenoxy)ethyI group), an alkoxy group having from 1 to 22 carbon atoms (for example, a methoxy group, a butoxy group, an octyloxy group, a dodecyioxy group, a hexadecyloxy group, a 2-dodecyloxyethoxy group) or an aryl group (for example, a phenyl group, an (x- or Pnaphthyl group, a p-tolyl group).

R3 in formula (1) represents a hydrogen atom, a hydroxy group, or a halogen atom, an alkyl group, an alkoxy group, or an aryl group, each as defined for R2 above. At least one of R2 and R3 is an alkoxy group.

R4 in formula (11) represents an alkyl group having from 1 to 22 carbon atoms (for example, a methyl group, a propyl group, a 2-ethylhexyl group, a dodecyl group, a hexadecyl group, a 2-(2,4-di-tert-amyiphenoxy) ethyl group, a 2-dodecyloxyethyl group) or an aryl group (for example, a phenyl group, an a- or P-naphthyl group, a 4-tolyl group).

R5 in formula (11) represents a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom), an alkyl group having from 1 to 22 carbon atoms (for example, a methyl group, an ethyl group, a tert-butyl group, a benzyi group, a 2-(2,4-di-tertamylphenoxy)ethyI group, a tetradecyl group), an alkoxy group having from 1 to 22 carbon atoms (for example, a methoxy group, a 2-ethylhexyloxy group, an octyloxy group, a 2-dodecyloxyethoxy group, a hexadecyloxy group), or an aryl group (for example, a 30 phenyl group, an aorp-naphthyl group, ap-tolyl group).

Of the couplers represented by formulae (1) and (11), those in which the total number of carbon atoms included in the groups represented by R2 and R3 is at least 6, and those in which the total number of carbon atoms included in the groups represented by R4 and R5 is at least 4, are particularly preferred for achieving the objects of the present invention.

Specific examples of the typical couplers according to this invention are shown below.

(1) 1 c 13 H, 7 CON14 Ct CH 3 Nil ',0C 12 11 25 N'-N 0 C"c, CL cú OC 12 H 25 02 NH, 5 0 C H CON11 El, cú 13 27 IN 0 cú cú Ci 4 GB 2 086 597 A 4 (3) (4) (5) (6) (7) c L OC H \ 12 25 0- \ NH 17- S -Q 1 c 11 CON1i C11 13 27 N 0 j cl If CL CL c 18 11 35 0 N 0 r7r - CL oc 14 11 79 WIT CH 3 N N "0 c L c L CL c 4 H 9 0 C 11 11(t) C13 27 Nil S H CONH N, 0 c 5 11 11(t) c ú-tc L 1 LL c 13 H 27 CONII c 2 c ú c 4 lib PNII, fl S N, c 11 I:N:f:0 8 17 ci, CL CL / oi\ Nil, FI 0 N 0 N:NJ, z 0 C81117(t) rIT c ",o c L CL 1 A GB 2 086 597 A 5 (8) (9) k1a) (11) (12) cl CC a H 17 0 NH S If 11 10 CF 3 w,'S oc 8 H 17 CL 1 lc L 1 L ú c 91 oc H Nil S C4 119 (t) ClYO2 0 oc 8 H 17 ci,oc CL CL oc H \ 8 17 Cú0\ Nill- S'Doc 8 11 17 CL N IN --'0 CLOC, ocil, CL OC H \ 10 21 N[1, 5 Q CH 1 3 11 C-NH oc H N C13 27 11 ' 0 10 21 0 CL, CL CL CL qC H \ 5 11 N1lr 'SQ\ 1 c 11 SONil CH is 37 0 3 ci CL 6 GB 2 086 597 A (13) (14) (15) cl()) (17) 6 CL 2 oc 12 11 25 CL CL IN;zo ci ú c L c 14 H 29 0 CL 011 c 4 11 9 (t) ONH 1 c 14 11 29 NHd 11 N IN '0 oc 8 11 17 0 CL CL 1: 1 1 L CL OC 8 H 17 NH c 4 H 9 (t) c Ii CONH N,011 9 19 N 0 ci cú cl CL ONH V1 c 6 Ill 3 (t) S OCII C 11 CONII N j: c 11 13 27 IN 0 6 13 CLIOCL CL (0c 5 H 11 0-(CH 2)3 -N-SO 2 -\=C 1 c 5 H 11 CH 3 CL 0C10H21 S c 4 H 9 N 0 1 C Y.' C L CL a z 7 r (18) (19) GB 2086597 A 7 CL c Nlir- S.OOC 12 H 25 Q -CHCONH ",41 (t)C 5 H 1 1 0 CL c 5 H 11(t) 0 CL,Oct CL c 14 H 29 O-C 11 0 (20) (22) CL OC 4 H 9 NH S N,NJ-,o c j CL Qr CL CL 8 1-117(t) OCH OC 11 3 4 9 NH 5 -Q c 4 Hq (t) c 13 11 27 CONH NN,5, 0 Cú,oct CL CL OCII,CH OCH 2 3 Nil S CL,, ' 0 c 8 H 17 (t) CL,Oct CL CL OC 4 119 Nil 0C4 11 9 S-0 Hq (t) c 13 11 27 CONII N 'N10 C4 CL 0 CL CL 8 GB 2 086 597 A 8 (23) CL oc H ONH "IF Sc 4 H 9 (t) c 13 11 27 CONII N_10 oc 8 H 17 CL 1 CL ' Q-', w CL (24) CL OC H \ 4 9 ONH S C H ONH OC H 13 27 0 4 9 ci,Oct C 1 C:5) C OC H CL -ONH - 4 9,,f N c 11 -N 'O 8 17 1 CL (26) CL OC H 12 25 Ni S 0 N 0 0 C4 Hq (t) --c:r ctoct cl (27) 1 c fl,'CoNfi 1-5 1 CL c 4 H 9 0 oc 4 H 9 s N, N -3k 0 ci CL CL c 4 H 9 (t) 9 GB 2 086 597 A 9 (28) CL c 13 H 27 CONH (29) (30) (31) (32) c 8 H 17 0 CL ONH S/ 0 c 4 H9 C1,0CR CL CL OC 12 H 25 Ni S 1 k c 13 Il 27 CONII N4 5Wz 0 1 c x 1: f c L c L C,li 5 CONII c L 0 Nil oc 12 H 25 V_ S 0 \ cIl i o 2 0 CL CL 1 CL c 4 11 9 (t) CL 1 CL 3 Nil S oc 12 11 25 CLi 'CL CL CL Nil S oc 6 11 13 c 13 H 27 CONII 0 - CL CL 0C61113 1 f CL GB 2 086 597 A (33) (34) (35) (36) (37) c 14 H 29 O-C 11 0 CL c 4H9 (t) NH S 0 N oc IN 4H9 C11 CL C4 Hq (t) CL CL 0 NH TI S _ oc 6 H 13 0 X N 1 0 C ú C ú 0C6 H 13 c is H 37 1 c ú c 1 N H S C131127CONH 0 01- H Ocú C13 27 CL CL c 4 H 9 (t) ONII S oc 8 H 17 HO O-CHCONH 1 ctoct c 4 [19(t) -12"25 CL CL CLfHq(t) CL -ONH 0 C 3117 CL I:N0 C oc C 3117 C4Hg(t) CL 11 (38) (39) (40) (41) (42) 1 Cl 3112 7 CNIA 0 C 17 H 35 CNfl U 0 CL C 4 H 9 (t) NH H C 12 11 25- 0- (C11 2)3 NHS02 % oc 4 9 Cú1 CL C 4 Hg(t) C ú C zoc 4 H 9 Nil C N, C H -,N,, 0 8 17 C,OC, CL CL Cl-ONH oc 8 11 17 S oc 8 H 17 C" "C ' CL CL oc 11 4 9 ONH S-0 N7, 3 CL -OCII 3 CH 3 C 8 11 17 (t) CL oc H \ 8 17 Nil,- S -Q CL -01 1 1 1 N - C H ' 'N'z 0 8 17 (t) ci CL CN GB 2 086 597 A 11 12 GB 2 086 597 A 12 (43) CL OC 8 H 1,7 ONH S CL K,, -0 c 8H 17 c L_ C.:rl 1 CO0C14H 29 (44) CL OC H 15 ONH 1 S c 13 11 27 CNII 1 UN' 0 c 8 H 17(t) 20 11 0 _tCL CL 25 (45) CL C H 0 H 8 17x OC 8 17 NH S 30 0 N 0 c 8 H 17 (t) c H)::I CH 3-OCL 18 35 35 OC 8 11 17 The couplers used in the present invention can be synthesized from thiophenol derivative which corresponds to the desired coupling releasable group and a so-called 4-equivalent couplers, in which the coupling active position is unsubstituted, according to the following methods.

1. Athiophenol derivative or a corresponding disulfide is converted into a suphenyl halide by treatment with a haloenating agent (for example, chlorine, bromine, sulfuryl chloride, N-bromosuccinimide), and then the sulphenyl halide is reacted with a 4-equivalent coupler in the presence of a basic catalyst, or in the absence of a catalyst, to introduce an arylthio group to the coupling active position of the coupler as set forth in Reaction Scheme I below. This method can also be conducted by the addition of a halogen (i.e., halogen in a form of gas or liquid) in a mixture of a thiophenol derivative and a 4-equivalent coupler. This method is described in U.S. Patent 3,227,554.

Reaction Scheme I Ar 3_ SH is or z i (Ar 3_ S -, Ar 2 -NH- N, M jk 3 0 Ar 2 -NIII- -Ar Ar [N Ar 13 wherein Ar 2 represents a group of J and Ar 3 represents a group of h 10 X (R)m, K 2 \ -u or a group of R3) M 2 R 4 -Ct (R5), where X, R,, R2t 23, R4, R5, M1, M2 and n are the same as defined forthe formulae (1) and (11), GB 2 086 597 A 13 - 5 2. After the amino group of a 4-equivalent coupler is protected by acylation (for example, an acetyl group, an ethoxycarbonyl group, etc.), the active position thereof is treated with a halogenating agent and the resulting halogen substituted compound is reacted with a thiophenol derivative in the presence of a basic catalyst, or in the absence of a catalyst, to introduce the arylthio group to the coupling-active position of the coupler. By removing the protective group, the desired 2- equivalent coupler is obtained, as set forth in 25 Reaction Scheme 11 below. This method can be carried out in the manner similar to the method described in Japanese Patent Application (OP1) No. 91862/77 (the term "OH" as used herein refers to a "published unexamined Japanese patent application").

Reaction Scheme 11 Ar 2_ NH - 11 N,,H3 0 Ar 1 X 2 COR Ar 2_1 N it IN Jo, 1 1 Ar COR 3_ 1,,:,,S-Ar 3 Ar SH Ar -N N 0 Ar COR RCOX Ar 2 0 Ar Ar 2_ N"TI:l S -Ar-1 IN4 1 1 0 Ar 14 GB 2 086 597 A 14 The thiophenol derivative or the corresponding disulfide, which is the source of the coupling releasable group, can be synthesized according to the following methods.

3. A corresponding aniline derivative is reacted with sodium nitrite under an acidic condition to form the diazonium salt, an then the latter is reacted with sodium sulfide or sodium disulfide to obtain a thiophenol derivative or a corresponding disu [fide, respectively, asset forth in Reaction Scheme III below. This method is described in S.R. Sandler, W. Karo, Organic Functional Group Preparations, pp. 480-485, Academic Press (1968).

Reaction Scheme N NaN02 Ar 3 NH2 A0NOW6 2 HW Ar'SH or (AP-S+r- 0.

101 Na2S or Na2S2 4. A benzene derivative including a subtituent suited for the purpose of this invention is chlorosulfonated 20 with chlorosulfonic acid, and then the resulting compound is reduced using metallic zinc or metallic tin and an acid, to obtain a thlophenol derivative as set forth in Reaction Scheme IV below. This method is described in S.R. Sandier, W. Karo, Organic Functional Group Preparations, pp. 480- 485, Academic Press (1968).

Reaction Scheme IV CtS03H Ar'H Ar 3SO2ce ZnorSn ArSH 0 This method is applicable to a sulfonyl chloride which is produced by reaction of a corresponding sulfonic acid with thionyl chloride, phosphorus oxychloride, etc., when an appropriation sulfonic acid is available as a starting material. Also, it is possible to obtain a corresponding disulfide using hydrogen iodide as a reducing 40 agent.

5. After converting a corresponding phenol derivative to a sodium salt, the latter is reacted with dimethylthiocarbamoyl chloride to form a dimethylthionecarbamate, and the resulting compound is subjected to heat rearrangement and hydrolysis through a dimthylthiolca rba mate to obtain a thiophenol derivative as set forth in Reaction Scheme V below. This method is described in J. Org. Chem., Vol. 31, p. 4Ei 3980 (1956).

Reaction Scheme V S (CH3)2NCCt' 11 M OCN(CH3)2 AP-ONa 0 11 80H AOWN(CH3)2 Ar'SH so Synthesis examples of typical compounds according to this invention are set forth below, but other 60 couplers can be synthesized by the combination of the synthesis methods generally described below.

GB 2 086 597 A is SYNTHESIS EXAMPLE 1 Synthesis of 1-(2,4,6-trichlorophenyl)-4-(5-chloro-2-dodecyloyphenylthio)3-(2-chloro-5-t etradecanamido- anilino)-2-pyrazoline-5-one [Coupler (2)1:

(i) Synthesis of 5-chloro-2-dodecyloxythiophenol A mixture of 28.3 g of pchlorophenol, 52.5 g of tetradecyl bromide and 50 9 of potassium carbonate was 5 heated in 150 me of acetone for 20 hours with stirring. After cooling, the reaction mixture was poured into ice water. The crystals thus-deposited were collected by filtration, washed with water, washed with methanol and dried to obtain 54.8 g of the crystals.

29.7 9 of the above-described crystals was dissolved in 120 me of chloroform and to the solution was added dropwise 20 mie of chlorQsulfonic acid under cooling with ice. After stirring for 2 hours at room 10 temperature, the reaction mixture was poured into ice water. The organic layer was separated, washed with an aqueous saturated sodium chloride solution and chloroform was distilled off under reduced pressure. To the residue were added 180 g of ice water, 35 me of surfuric acid, and 31. 2 9 of zince powder, and the mixture was stirred at 800C for 2 hours. After cooling, the residual zinc was removed by filtration and the mixture was extracted with ethyl acetate. The extract was washed with an aqueous saturated sodium chloride solution 15 and ethyl acetate was distilled off under reduced pressure. The residue was separated through a column with a silica gel (using hexane as a spreading agent) to obtain 25 g of the oily desired product.

(ii) Synthesis of Coupler (2) 15 9 of 5-chforo-2-dodecyloxythiophenol was dissolved in 40 m,9 of methylene chloride, and to the 20 solution was added dropwise 4.2 me of sulfury] chloride. After stirring at room temperature for 45 minutes, the solvent was distilled off to obtain red colored oily sulphenyl chloride.

9 of 1-(2,4,6-trichic)rophenyi)-3-(2-chloro-5-tetradecanamidoanilino)-2pyrazolin -5-pyrazolin-5-one was dissolved in 100 m.0 of methylene chloride and to the solution was added 17.5 g of triethylamine. To the resulting mixture was added a solution of the sulphenyl chloride obtained above dissolved in 20 me of methylene chloride. After stirring at 400C for 2 hours, the solvent was distilled off under reduced pressure, and the residue was dissolved in a warm mixture of ethyl acetate and ethanol. The solution was washed with diluted acetic acid, and then with aqueous saturated sodium chloride, and then the solvent was distilled off under reduced pressure. The residue was recrystallized twice from a mixture of ethyl acetate and acetonitrile, to obtain 27 g of the desired coupler. The melting point was 160 to 1610C.

Elemental Analysis:

Calculated: C: 59.97%, H: 6.75%, N: 5.95% Found: C. 59.74%, H: 6.70%, N: 5.93% SYNTHESIS EXAMPLE 2 Synthesis of 1-(2,4,6-trichlorophenyl)3-(2-chloro-5tetradecanamidoanilino)-4-(2,5-di-te rt-hexyl-4methoxyphenylthio)-2pyrazolin-5-one [Coupler (16) described above]: (1) Synthesis of 2,5-ditert-hexyl-4-methoxythiophenoI 50 g of 2,5-di-tert-hexyi-4-methoxyphenoI was dissolved in 500 m,' of toluene, and to the solution was added 11 g of potassium hydroxide. After removing water under refluxing by heating, to the residue was added dropwise melted dimethylthiocarbamoyl chloride. After stirring with heating for 2 hours, the toluene was distilled off and the residue was poured into 45 water. The mixture was extracted with ethyl acetate, washed with water, and the ethyl acetate solvent was distilled off under reduced pressure. The residue was dissolved in 30 me of sulfolane (i.e., tetrahydro-1,1 dioxidethiophene) and the solution was heated at 27WC for 1 hour while stirring. After cooling, ethyl acetate was added to the mixture, the mixture was washed with water, and the solvent was distilled off under reduced pressure, To the residue were added 200 me of methanol and 20 g of potassium hydroxide, and the 50 mixture was refluxed for 2 hours by heating. After cooling, the mixture was acidified with hydrochloric acid and extracted with ethyl acetate. After washing with water, the solvent was distilled off under reduced pressure and the residue was crystallized from methanol to obtain 12.5 g of the desired compound.

(5) Synthesis of Coupler (16) 24 g of the desired coupler was obtained in an analogous manner to that described in step (5) of Synthesis Example 1, using 12.5 g of 2,5-di-tert- hexyi-4-methoxythiophenoI and 22 g of 1-(2,4,6-trichlorophenyl)-3(2chforo-5-tetradecanamidoanilino)-2-pyrazolin-5 -one. The melting point was 183 to 185'C.

Elemental Analysis:

Calculated: C: 62.60%, H: 7.22%, N: 6.08% Found: C: 62.64%, H: 7.38%, N: 6.10% 16 GB 2 086 597 A 1.6 The magenta coupler of the formula (I) or (11) preferably is coated in an amount of 2 X 10-3molto5x 10-1 mol, preferably 1 X 10-2 mol to 5 X 10-1 mol, per mol of silver.

The photographic emulsion layer of a photographic light-sensitive material according to this invention can contain other color-forming couplers, that is, a compound capable of forming a dye upon oxidative- coupling with an aromatic primary amine developing agent (for example, a phenylenediamipp. derivative, an aminophenol derivative) in color development processing, in addition to a coupler according to the present, invention. For instance, a 5-pyrazolone coupler, a pyrazolobenzimidazole coupler, at cyanoacetyl chroman, coupler and an open-chain acylacetonitrile coupler can be used as a magenta-dye:%forming goupler, an - -. acylacetamide coupler (for example, a benzoyl acetanilide, pivaloyl acetanilide), can be,used as a yellow coupler; and a naphthol coupler and a phenol coupler can be used as a cyan-dye-forming coupler. A non-diffusible couplerwhich contains a hydrophobic group, called a ba - [last group, in the rpolec.ule thereof is preferred as a coupler. These couplers can be 4-equivalent or 2equivalent. In addition, a colored coupler providing a color correction effect, or a coupler which releases a development inhibitor upon development (a so-called DIR coupler).can also be preserittherein. Also; in addition to a DIR coupler, acolpriess DIR coupling, compound which provides a colorless product upon the coupling reaction and releases.-a development-,_ inhibitor can be present in the photographic light-sensitive material.

Specific examples of the magenta color-forming couplers which can be employed are those described, for example, in U.S. Patents 2,600,788,2,983,608,3,062,653,3,127,269,3,311, 476,3,419,391'1 3,519,429, 3,558,319,3,582,322,3,615,506,3,834,908 and 3,891,445, West German Patent 1,810,646, West German Patent Application (OLS) Nos. 2,408,665,2,417,945,2,418,959 and 2,424,467, Japanese. Patent Publickions 20 No. 6031/65-, Japanese Patent Applications (OPI) Nos. 20826/76,58922/77, 129538/74,74027/74,159336/75, 4212ln7,74028174,60233/75, 26541/76 and 55122/78, and so forth. Specific examples of the yellow color-forming couplers which can be emplo

yed are those described, for example, in U.S. Patents 2,875,057,3,265,506,3,408,194,3,551,155,3,582, 322,3,725,07 and 3,891,445,,West German Patent 1,547,868, West German Patent Application (OLS) Nos. 2;219, 917,2,261,361 and2,414,006, 25 British Patent 1,425,020, Japanese Patent Publications No. 10783/76, Japanese Patent Applications (OPI) Nos. 26133/72,73147/73,102636/76,6341/75,123342/75,130442/75,21827/76, 87650/7.5,8 2424/77 and 115219/77, and so forth.

Specific examples of the cyan color-forming couplers which can be employed are those described, for example, in U.S. Patents 2,369,929,2,434f272,2,474,293,2,521,908,2,895, 826f 3fl34,892,3,311,476, 30 3,458,315,3,476,563,3,583f971, 3,591,383, 3,767,411 and 4,004,929, West German Patent Applications (OLS) Nos. 2,414,830 and 2,454,329, Japanese Patent Applications (OPI) Nos. 59838/73, 26034/76,5055/73, 146828/76f 69624/77 and 90932/77, and so forth.

Specific examples of the colored couplers which can be employed are those described, for example, in U.S. Patents 3,476,560, 2,521,908 and 3,034,892, Japanese Patent Publication Nos. 2016/69,22335/63, 11304/67, and 32461/69, Japanese Patent Application (OPI) Nos. 26034/76 and 42121/77, West German Patent Applications (OLS) No. 2,418,959, and so forth.

Specific examples of DIR couplers which can be employed are those described, for example, in U.S.

Patents 3,227,554,3,617,291f 3,701,783,3,790,384 and 3,632,345, West German Patent Applications (OLS) Nos. 2,414,006,2,454,301 and 2,454,329, British Patent 953,454, Japanese Patent Applications (OPO Nos. 40 69624/77,122335/74, Japanese Patent Publication No. 1.6141/76, and so forth.

As noted abover in addition to a DIR coupler, other compounds which release a development inhibitor upon development can also be present in the light-sensitive material. For example, DIR compounds as - described, for example, in U.S. Patents 3,297,445 and 3,379,529, West German Patent Application (OLS) No.

2,417,914 and Japanese Patent Applications (OPI) Nos. 15271n7 and 9116n8 can be employed. 45 Known methods, for example, the method described in U.S. Patent 2,322,027, can be employed to incorporate the coupler into the silver halide emulsion layer. For example, the coupler ca n be dissolved in a phthalic acid alkyl ester (e.g., dibutyl phthalate, dioctyl phthalate), a phosphoric acid ester (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctylbutyl phosphate), a cirtic acid ester (e.g., tributyl acetylcitrate), a benzoic acid ester (e.g., octyl benzoate), an alkyl amide (e.g., diethyl laurylamide), a fatty acid 50 ester (e.g., dibutozyethyl succinate, dioctyl azelate), a trimesic acid ester (e.g., tributyl trimesate); or an organic solvent having a boiling point of from about 30 to 150'C such as a lower alkyl acetate (e.g., ethyl acetate, butyl acetate), ethyl propionate, sec-butyl alcohol, methyl isobutyl ketone, P-ethoxyethyl acetate or 2-methoxy ethyl acetate. Then the solution is dispersed in a hydrophilic colloid. The above-described or ganic solvents having a high boiling point and the above-described organic solvents having a low boiling point 65 may be used as mixtures, if desired.

Furthermore, the dispersing method using a polymeric material as described-in Japanese Patent Publication No. 39853/76, Japanese Patent Application (OPI) No. 59943/76 can also be used.

When a coupler having an acid group, such as a caroxylic acid group or a sulfonic acid group, is used, it can be incorporated in a hydrophilic colloid as an alkaline aqueous solution thereof.

The photographic light-sensitive material prepared according to the present invention can also contain, as a color fog preventing agent, a hydroquinone derivative, an aminophenol derivative, a galliC'acid derivative or an ascorbic acid derivative. Specific examples of these agents are described in U.S. patents 2,360,290, 2,336,327, 2,403,721, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728, 659, 2,732,300 and 2,735,365, Japanese Patent Applications (OPI) Nos. 92988/75,92989n5,93928/75, 110337/75 and 146235/77, Japanese 65 10, 17 GB 2 086 597 A 17 Patent Publication No. 23813/75, and so forth.

The hydrophilic colloid layers of the photographic light-sensitive material prepared in accordance with the present invention can also contain an ultraviolet absorbent. For example, a benzotriazole compound substituted with an aryl group, a 4-thiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, butadiene compound, a benzoxazole compound or an UV absorbing polymer can be employed. These UV absorbents may be fixed in the above-described hydrophilic colloid layer, if desired.

Specific examples of UV absorbents which can be employed are those described, for example, in U.S. Patents 3,533,794,3,314,794 and 3,352,681, Japanese Patent Application (OPI) No. 2784/71, U.S. Patents 3,705,805,3, 707,375,4,045,229,3,700,455 and 3,499,762, West German Patent Publication No. 1,547,863, and so forth.

In the practice of the present invention, known color fading preventing agents as described below can be employed. The color fading preventing agent can be used individually or in a combination of two or more thereof. Known color fading preventing agents include a hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols,p-oxyphenol derivatives and bisphenols.

Specific examples of the hydroquinone derivatives are described, for example, in U.S. Patents 2,360,290, 15 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300, 2,735, 765, 2,710,801 and 2,816,028 and British Patent 1,363,921. Specific examples of the gallic acid derivatives are described, for example, in U.S.

Patents 3,457,079 and 3,069,262. Specific examples of thep-alkoxyphenols are described, for example, in U.S. Patents 2,735,765 and 3,698,909, Japanese Patent Publication Nos. 20977/74 and 6623/77. Specific examples of the p-oxyphenol derivatives are described, for example, in U. S. Patents 3,432,300,3,573,050, 20 3,574,627 and 3,764,337, Japanese Patent Application (OPI) Nos. 35633/77, 147434/77 and 152225/77, Specific examples of the bisphenols are described, for example, in U.S. Patent 3,700,455.

In the photographic light-sensitive material prepared in accordance with the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain therein a dispersion of a water-insoluble or water-sparingly-soluble synthetic polymer for the purposes of improving dimensional 25 stability and so forth. Synthetic polymers which can be used include a polymer derived from a monomer unit comprising an alkyl acrylate or methacrylate, an alkoxyalkyl acrylate or methacrylate, a glycidyl acrylate or methacrylate, an acrylamide, a methacrylamide, a vinyl ester (e.g., vinyl acetate), acrylonitrile, an olefin or styrene, individually or in a combination thereof, and a copolymer derived from a monomer unit as described above and a monomer unit comprising acrylic acid, methacrylic acid, an a,p-unsaturated 30 clicarboxylic acid, a hydroxyalkyl acrylate or methacrylate, a sulfoalkyl acrylate or methacrylate or styrenesulfonic acid.

A photographic emulsion layer or other hydrophilic colloid layer of the photographic light-sensitive material prepared in accordance with the present invention can contain a whitening agent, such as a stilbene, a triazine, an oxazole, or a cournarin. These agents can bewater-soluble, or can be employed as a 35 dispersion of the water-insoluble whitening agent. Specific examples of fluorescent whitening agents are described in U.S. Patents 2,632,701, 3,269,840 and 3,359,102, and British Patents 852,075 and 1,319,763, Research Disclosure, Vol. 176, No. 17643, p. 24, leftside column,,ee. 9- 36, "Brighteners" (December, 1978).

In photographic processing of the photographic light-sensitive material prepared the present invention, any known methods can be used. Known processing solutions can be used. The processing temperature is 40 usually selected within the range of from 18'C to 50C. However, temperatures lowerthan 18'C and temperatures higher than 50'C can be employed, if desired. According to the particular purpose, either a development processing for forming a silver image (black-and-white photographic processing) or a color photographic processing comprising a development processing for forming a dye image can be used.

As a fixing solution, a solution having a composition generally used can be used. Afixing agent which can 45 be used includes a thiosulfuric acid salt and a thiocyanic acid salt. Additionally, an organic sulfur compound which is known to have the effect as a fixing agent can be used. The fixing solution may contain therein a water-soluble aluminum salt as a hardener.

Conventional methods can be employed for forming a dye image. Among methods that can be employed are: (1) a negative-positive method, for example, as described in Journal of the Society of Motion Picture and 50 Television Engineers, Vol, 61, pp. 667-701 (1953); (2) a color reversal method which comprises developing with a developer containing a black-and-white developing agent to form a negative silver image, then subjecting the photographic material to at least one uniform exposure or to another appropriate fogging treatment, and subsequently performing color development to obtain positive dye images; and (3) a silver dye bleaching method which comprises exposing a dye-containing photographic emulsion layer and 55 developing the same to form a silver image and then bleaching the dyes using the silver image as a bleaching catalyst.

The color developer generally comprises an alkaline aqueous solution containing a color developing agent. Suitable color developing agent which can be employed includes a known primary aromatic amine developing agent, e.g., a phenylenediamine (e.g., 4-amino-N,N- diethylaniline, 3-methyl-4-amino-N,N diethylaniline, 4-amino-N-ethyl-N-0-hydroxyethylaniline, 3-methyl-4-amino- N-ethyl-N-p hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-pmethanesulfamidoethylaniline or 4-amino-3-methyl-N ethyl-N-p-methoxyethylaniline).

In addition, a developing agent described in L.F.A. Mason, Photographic Processing Chemistry, at pages 226 to 229, Focal Press (1966), U.S. Patents 2,193,015 and 2,592,364 on Japanese Patent Application (OP1) NO. 65 18 GB 2 086 597 A 18 64933/73 can be employed.

The color developer can also contain a pH buffering agent, such as a sulfite, a carbonate, a borate, or a phosphate of an alkali metal, a developing inhibitor or an anti-fogging agent such-as a bromide, an iodide or an organic anti-fogging agent. In addition, if desired, the color developer can also contain a water softener; a preservative such as hydroxyiamine; an organic solvent such as benzyl alcohol or diethylene glycol; a developing accelerator such as polyethylene glycol, a quaternary ammonium salt, an amino; a dye-forming coupler; a competing coupler; a fogging agent such as sodium borohydride; an auxiliary developer such as 1-phenyl-3-pyrazolidone; a viscosity- imparting agent; a polycarboxylic acid type chelating agent described in U.S. Patent 4,083,723; an anti-oxidizing agent as described in West German Patent Application (OLS) No.

2,622,950; or other additives.

The photographic emulsion after color development are generally bleachprocessed. Bleach processing can be performed at the same time as fixing, or separately therefrom. Suitable bleaching agents which can be employed include a compound of a polyvalent metal such as iron (111), cobalt (IV), chromium (VI) or copper (11), a peracid, a quinone or nitroso compound. Specific examples include a ferricyanide; a bichromate; an organic complex of iron (111) or cobalt (IV); an aminopolycarboxylic acid such as ethylenediaminetetraacetic 15 acid, nitrilotriacetic acid or 1,3-diamino-2-propanol tetraacetic acid; a complex of an organic acid such as citric acid, tartaric acid or malic acid; a persulfate; a permanganate; and nitroso phenol. Of these, a. particularly useful bleaching agent is potassium ferricyanicle, sodium ethyl enediaminetetraacetate iron (111) or ammonium ethyl enedia mi netetraacetate iron (111). Ethyl ened iaminetetraacetate iron (111) complex is useful both in a bleaching solution and in a monobath bleach-fixing solution. - A bleaching or bleach-fixing solution can contain various additives, including a bleach accelerating agent as described in U.S. Patents 3,042, 520 and 3,241,966, Japanese Patent Publications Nos. 8506/70 and 8836/70 or a thiol compound as described in Japanese Patent Application (OPI) No. 65732/78.

The photographic light-sensitive material prepared using the present invention maybe subjected to - - processing with a-developing solution which is replenished or otherwise maintains its properties by the 25 methods as described in Japanese Patent Applications (OPI) Nos. 84636/76, 119934/77,46732/78,9626/79, - 19741/79 and 37731/79.

The photographic light-sensitive material prepared using the present invention may be.processed with a - bleach-fixing solution which can be subjected to regeneration treatment, such as by methods as described in Japanese Patent Applications (OPI) Nos. 781/71,49437/73,18191/73, 145231/75,18541/76,19535/76 and 30 144620/76 or Japanese Patent Publication No. 23178/76.

The present invention is illustrated in greater detail by reference to the following examples.

101 Example 1

10 g of Cp-A (a magenta coupler illustrated inTable 1)wasdissolved in a mixture of 20 me oftricresyl phosphate and 20 me of ethyl acetate, and the resulting solution was dispersed in 80 g of a 10% aqueous gelatin solution containing sodium dodecylbenzenesulfonateto obtain an emulsified dispersion. Then, this - emulsified dispersion was mixed with 150 g of a green-sensitive silver chlorobromide emulsion (bromide: 50 mol%) (containing 8.8 g of silver), sodium dodecylbenzenesulfonate was added as a coating aid and it was coated on paper support both sides of which were laminated with polyethylene, Further, on this layer, a 40 gelatin coating solution was coated (gelatin 1 g/M2) as a protective layer, and dried to prepare Sample 1.

Sampis 2 to 14were prepared in the same manner as described above, except for changing the amount of the green-sensitive silver chlorobromide emulsion added to 75 g, an changing the coupler and amount thereof to those set forth in Table 1 below.

These samples were exposed to light at 1,000 lux/sec using a sensitometer, and then processed in the 45 following processing solutions.

1 19 GB 2 086 597 A 19 Color Developer Solution Benzyl Alcohol 15 me Sodium Sulfite 5 g 5 Potassium Bromide 0.4 g Hydroxylamine Sulfate 2 g 1.10 4-Amino-3-methyl-N-ethyl-N-[P- 6 g 10 (methanesulfonamido)ethyll-pphenylenediamine Sodium Carbonate Monhydrate 30 g 15 Waterto make 1,000 mf (pH 10.1) 20 Bleach-Fixing Solution Ammonium Thiosulfate (70% aq. soin.) 150me 25 Sodium Sulfite 15g Sodium Ferric Ethylenediamine- 40 g tetraacetate 30 Ethyl enedia mi netetraacetic Acid 4 g Water to make moo mie (pH 6.9) 35 Processing Step Temperature Time rc) 40 Color Development 33 3 min 30 see Bleach-Fixing 33 1 min 30 see 46 Washing 28 to 35 3 min 45 Each of these samples in which dye images had been thus formed was subjected to a fading test for 5 days using a Xenon fading tester (200,000 lux) equipped with an ultraviolet light-absorbing filter, absorbing light of a wavelength of 400 nm or shorter (manufactured by Fuji Photo Film Co., Ltd.). The measurement of the 50 optical density of the color image and color stain was carried out using a Macbeth Densitometer with a Status AA filter. ("Macbeth" and "Status" are registered Trade Marks). The results of the measurement are shown in Table 2 below.

N C) TABLE 1

Sample No. Structure of Coupler 1 2 Amountof Coupler Coupler No. Added Cp-A 10.0 g C13H27CON11 c 91 MIT1 7-., 0 N ct U c 91 C2145 CO0C2H5 1 S (OC4119 U U h G U N ri O-CC4Hg(t) CoatedAmount of Silver CoatedAmount of Coupler Remarks (Mg/M2) Mg/m 2 3301375 Cp-B 11.7 g 1651440 Comparison Comparison 11 11 NJ Q 3 4 TABLE 1 (Cont'd) Sample No. Structure of Coupler c 2, C13H27CON-H CH300C CO0C2H5 NH7,:- S N N 'N 0 ct 111 1 c z 1-1 c L :2:>NH - S -Q 1 C14300C TN:"O COMC 181137 cz c 91 c z Coupler Coupler No. Added CP-C 12.9 g CoatedAmount Amountof ofSilver CoatedAmount of Coupler Remarks (M9/M2) Mg/M2 165/484 Cp-D 14.2 g 1651532 Comparison Comparison TABLE 1 (Cont'd.) Sample No. Structure of Coupler CA 6 Amount of Coupler Coupler No. Added 1 NH S -WC 1 2H 2 5 C13H27CONH c z..1 1 c z c ú c z C13H27CONH 1 NH -Uf S -Q N 0 CONHClOH37 c 9,., U cú CoatedAmount of Silver CoatedAmount of Coupler Remarks Cp-E 14.5 g Mg1M2 (mg-/M-2) 165/543 Cp-F 16.3 g 165/612 Comparison Comparison N) N m U5 N C) CO C7) W1 CD j m to 1 1 TABLE 1 (Cont'd.) CoatedAmount Amountof ofSilver Sample Coupler Coupler CoatedAmount No. Structure of Coupler No. Added of Coupler Remarks Mg1M2 CL Mg/M2) 7 N S-C0C12H25 CP-G 14.8 g 1651553 Comparison C13H27CONH R-NJ"O CL CL CL CL NH S 0C12H25 CP-1 15.09 1651561 This N Invention C13H H '-N 'O 2 7C0 H CL.1.1 CL -1 1 CL r') W W N) 45 TABLE 1 (Cont'd.) CoatedAmount Amount of of Silver Sample Coupler Coupler CoatedAmount No. Structure of Coupler No. Added of Coupler Remarks (Mg1M2) c 9, 0C12H25 Mg1M 2 9 S Cp-2 15.3 g 165/574 This NH -1 - Invention C13H27CONH N c 9, cú ',.11 1 x 2, 1..

c 91 CP, 0C12H25 NH S -0 Invention Cp-3 15.0 g 165/561 This C131127CONH NNCO CH3 c P, c X 11 1 1 c L 0. 4 m.h 1...1 TABLE 1 (Cont'd) CoatedAmount Amount of of Silver Sample Coupler Coupler CoatedAmount No. Structure of Coupler No. Added of Coupler Remarks (Mg/M2) CL 0C4H9 Mg1M2 NH S - Cp-6 14.89 1651553 This C81417 (t) Invention C13H27CONH lN''O c ú", 11.1 1 c 9, 1-1 CL CA 0C8H17 12 NH S /' C4Hg(t) Invention Cp-23 16.6 g 165/620 This 0C8H 11 C131127CONH Mj'N5Z 0 17 c A. 1 Ct 1 1 CA N) ul i G) W h> C W (3) (n W 'i W (n N) a) TABLE 1 (Cont'd.) Sample No. Structure of Coupler CA 13 14 0C4H9 1 \ CL- N, 0 U G8H17(t) cú 0C12H25 NH71 - S N 'N:r"t Hq (t) 0 C4 c 91 c 91 c 9.

11.1 y Amount of Coupler Coupler No. Added Cp-25 11.69 CoatedAmount of Silver CoatedAmount of Coupler Remarks Mg/rn2). %g1M2 1651436 Cp-26 12.7 g 165/474 This Invention This Invention I 1 1 N (3) 27 GB 2 086 597 A 27 TABLE 2

After Xenon Irradiation for 5 Days Magenta Color Image Magenta Density Yellow Stain Density 5 Sample No. Drax (Initial Density of 1.0) on White Background

1 Comparison 2.10 0.75 0.35 2 Comparison 1.74 0.17 0.41 10 3 Comparison 2.02 0.23 0.52 4 Comparison 1.98 0.22 0.39 15 Comparison 2.23 0.35 0.36 6 Comparison 1.98 0.21 0.36 7 Comparison 2.31 0.43 0.48 20 8 Present 2.29 0.76 0.31 Invention 9 Present 2.30 0,78 0.30 25 Invention Present 2.25 0,86 0.29 Invention 30 11 Present 2.28 0.88 0.29 Invention 12 Present 2.21 0.91 0.30 35 Invention 13 Present 2.09 0.77 0.26 Invention 40 14 Present 2.11 0.81 0.26 Invention As is apparent from Table 1 above, 2-equivalent couplers are used in Samples 2 to 14, although a 45 4-equivalent coupler is used in Sample 1. In order to confirm the reduction in the amount of silver halide used which is one object of the present invention, the coating amount of silver was reduced in Samples 2 to 4 to one half of that in Sample 1.

It is apparent from the results shown in Table 2 that the nature of the releasing or coupling-off group of the coupler is very important for obtaining the desired Dmax using only half amount of silver, and that the couplers according to the present invention have a high color forming property which can allow reduction in the silver amount. On the other hand, it is very surprising that the light fastness of the magenta color images formed and the change of yellow density in white background depend largely on the structure of the releasing group among the couplers capable of reducing the amount of silver used. By this detailed investigation it has been found that releasing groups of an extremely specific nature can achieve the objects 55 of this invention.

Example2

On a paper support both surfaces of which were laminated with polyethylene were coated a first layer (undermost layer) to a sixth layer (uppermost layer) as shown in Table 3 in order to prepare a color photographic light-$ensitive material which is designated Sample 15. A coating composition for a third layer was prepared in accordance with the procedure as described in Example 1. Thus samples were prepared using the couplers as shown in Table 4.

These samples were exposed using a sensitometer to light of 1,000 lux/sec equipped with a green filter, SP-2 (made by Fuji Photo Film Co., Ltd.). The, these samples were subjected to the same processing as 65 28 GB 2 086 597 A 28 described in Example 1. Then the samples were subjected to a fading testfor 5 days using a Xenon fading tester (200,000 lux) in a manner analogous to Example 1. The results obtained are shown in Table 5 below.

TABLE 3

Sixth Layer: Gelatin (1,000 Mg1M2) (Protective layer) Fifth Layer: Silver chlorobromide emulsion (Br:

(red-sensitive 50 mol%; silver: 300 Mg1M2), 10 layer) Gelatin (1,000 Mg1M2), Cyan coupler' (400 Mg1M2), Coupler solvent' (200 Mg/M2) Fourth Layer: Gelatin (1,200 Mg/M2), (interlayer) Ultraviolet light-absorbing agent3 15 (1,000 Mg1M2), Ultraviolet light-absorbing agent solvent2 (250 Mg/M2) 20 Third Layer: Silver chlorobromide emulsion (Br:

(green-sensitive 50 mol%: silver: 330 Mg1M2), layer) Gelatin (1,000 Mg/M_2), Magenta coupler 4 (375 Mg/M2), Coupler solvent' (750 Mg1M2) 25 Second Layer: Gelatin (1,000 Mg/M2) Onterlayer) First Layer: Silver chlorobromide emulsion (Br; 30 (blue-sensitive 80 moi%; silver: 400 Mg1M2), layer) Gelatin (1,200 Mg/M2), Yellow cou pler6 (300 Mg1M2), Coupler solvent7 (150 Mg1M2) Support:

Paper support both surfaces of which were laminated with polyethylene 1 Coupler: 2-[ct-(2,4-Di-tert-pentyl phenoxy) butanam idol-4,6-dichi oro5-methyl phenol 2 Solvent: Dibutyl phthalate 3 Ultraviolet light-absorbing agent: 2-(2-Hydroxy-3-sec-butyi-5-tert- butyl phenyl) benzotriazole 4Coupler: 1-(2,4,6-Trichlorophenyi)-3-(2-chloro-5-tetradecanamido)anilino2-pyrazolin-5 -one (Cp-A) 45 Solvent: Tricresyl phosphate 6 Coupler: a-Pivaloyi-a-(2,4-dioxo-5,5'-dimethyloxazolidin-3-yi)-2-chloro5-[a-(2,4-di-t ertpentylphenoxy)butanamidolacetanilide 7 Solvent. Dioctyl butyl phosphate 1 3 A t 29 GB 2,086 597 A 29 TABLE 4

Amountof Sample Coupler Coupler CoatedAmountof No. No. Added Silver1Coupler Remarks 5 (g) (rng/M2/Mg/M2) 1 15 Cp-A 10.0 330/375 Comparison 16 Cp-E 14.5 1651543 10 17 Cp-G 14.8 165/553 18 Cp-2 15.3 1651574 Invention 15 19 Cp-6 14.8 165/553 Cp-23 16.6 1651620 TABLE 5

Xenon Irradiation for 5 Days Yellow Stain Sample Magenta Density Density in 25 No. (Initial Density of 2. 0) White Background Remarks

1.61 0.32 Comparison 16 0.73 0.33 30 17 0.86 0.45 18 1.70 0.29 Invention 19 1.80 0.27 35 1.85 0.27 40 It is apparent from the resultsshown in Table 5 above that the 2- equivalent magenta couplers according to the present invention can provide improved light fastness of color images, and also prevent the yellow discoloration of the white background due to light, by use together with a known magenta color image stabilizer.

Claims

1. A silver halide color photographic light-sensitive material comprising a support having thereon a photographic layer containing at least one magenta coupler represented by general formula (1) or ([I):- GB 2 086 597 A 3,0 X R2 1 H / \ NH "C - - (R,) MI _ NI 1 3.)M2, (I) - 5 - S _ "N",o 1 Ar M 10 NH H OR4 (II) ,a 1 -S (R5) n (R,) MI N "'NJ' '0 1 15 Ar wherein Ar represents a phenyl group substituted with at least one substituent selected from a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and a cyano group; X represents a halogen 20 atom or an alkoxy group; R, represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acylamino group, a sulfonamido group, a sulfamoyl group, a carbamoyl group, a diacylamino group, an alkoxycarbonyl group, an alkoxysulfonyl group, an aryloxysulfonyl group, an alkanesulfonyl group, an aryisuifonyl group, an alkylthio group, an arylthio group, an al kyloxyca rbonyl amino group, an alkylureido group, an acyl group, a nitro group, a carboxy group or a trifluoromethyl group; R2 represents a halogen atom, a hydroxy group, an alkyl group, an alkoxy'group or an aryl group; R3 represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group or an aryl group; at least one of R2 and R3 represents an alkoxy group; m, and M2 each represents an integerfrom 1 to 4; R4 represents an alkyl group or an aryl group; R5 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an aryl group; n represents an integerfrom 1 to 6; andwhen M1,M2ancin each is2ormore,each R,, R3and Rr, may 30 be the same or different.

2. A silver halide color photographic light-sensitive material as claimed in Claim 1, wherein the phenyl group represented by Ar is substituted with an alkyl group having from 1 to 22 carbon atoms.

3. A silver halide color photographic light-sensitive material as claimed in Claim 1, wherein the phenyl group represented byAr is substituted with an alkoxy group having from 1 to 22 carbon atoms.

4. A silver halide color photographic light-sensitive material as claimed in Claim 1, wherein the phenyl group represented byAris substituted with an alkoxycarbonyl group having from 2to 23 carbon atoms.

5. A silver halide color photographic light-sensitive material as claimed in any of Claims 1 to 4, wherein X is an alkoxy group having from 1 to 22 carbon atoms.

6. A silver halide color photographic light-sensitive material as claimed in any of Claims 1 to 5, wherein 40 the group R, includes an alkyl moiety having from 1 to 36 carbon atoms.

7. A silver halide color photographic light-sensitive material as claimed in any of Claims 1 to 5, wherein the group R, includes an aryl moiety having from 6 to 38 carbon atoms.

8. A silver halide color photographic light-sensitive material as claimed in any of Claims 1 to 7, wherein -45 R2is an alkyl group having from 1 to 22 carbon atoms.

9. A silver halide color photographic light-sensitive material as claimed in any of Claims 1 to 7, wherein R2 is an alkoxy group having from 1 to 22 carbon atoms.

10. A silver halide color photographic light-sensitive material as claimed in any of Claims 1 to 9, wherein R3 is an alkyl group having from 1 to 22 carbon atoms.

11. A silver halide color photographic light-sensitive material as claimed in any of Claims 1 to 9, wherein 50 R3 is an alkoxy group having from 1 to 22 carbon atoms.

12. A silver halide color photographic light-sensitive material as claimed in any of Claims 1 to 7, wherein R4 is an alkyl group having from 1 to 22 carbon atoms.

13. A silver halide color photographic light-sensitive material as claimed in any of Claims 1 to 7, wherein R5 is an alkyl group having from 1 to 22 carbon atoms.

14. A silver halide color photographic light-sensitive material as claimed in any of Claims 1 to 7, wherein R5 is an alkoxy group having from 1 to 22 carbon atoms.

15. A silver halide color photographic light-sensitive material as claimed in any of Claims 1 to 11, wherein the total number of carbon atoms included in the groups represented by R2 and R3 is at least 6.

16. A silver halide color photographic light-sensitive material as claimed in any of Claims 1 to 7 or 12 to 60 14, wherein the total number of carbon atoms included in the groups represented by R4 and R5 is at least 4.

17. A silver halide color photographic light-sensitive material as claimed in any preceding claim, wherein the photographic layer is a light-sensitive silver halide emulsion layer.

18. A silver halide color photographic light-sensitive material as claimed in Claim 17, wherein the light-sensitive silver halide emulsion layer is a green-sensitive silver halide emulsion layer.

t -35 z 1 31 GB 2 086 597 A 31

19. A silver halide color photographic light-sensitive material as claimed in Claim 18, wherein the photographic material further contains a blue-sensitive silver halide emulsion layer containing a yellow color- forming coupler and a red-sensitive silver halide emulsion layer containing a cyan color-forming coupler.

20. A silver halide color photographic light-sensitive material as claimed in Claim 19, wherein the yellow color-forming coupler and the cyan color-forming coupler are each 2-equivalent couplers.

21. A silver halide color photographic light-sensitive material as claimed in any preceding claim, wherein thecouplerof theformula (1) or(II) is coated in an amountof 2 X 10-3 molto 5 x 10-1 mol per mol of silver.

22. A silver halide color photographic light-sensitive material as claimed in Claim 1, substantially as 10 hereinbefore described with reference to any of Samples 2 to 14,18,19 or 20 of the Examples.

Printed for Her Majesty's Stationery Office, by Croydon Printing Company Limited, Croydon, Surrey, 1982. Published by The Patent Office, 25 Southampton Buildings, London, WC2A lAY, from which copies may be obtained.